Organic Chemistry Commons^™

Praseodymium Nitride Endohedral Metallofullerene As Donor In Photovoltaic Cells, Luis F. Gardea, Manuel N. Chaur, Luis Echegoyen

COURI Symposium Abstracts, Summer 2012

Trimetallic nitride template endohedral metallofullerenes (TNT EMFs) have been found to have structures and electronic properties that make them suitable for fields like molecular electronics. The particular compounds synthesized were the family of TNT EMFs Pr₃N@C_2n due to the relatively high yield of Pr₃N@C­₈₈ and even more due to its low first oxidation potential (0.06 V) and therefore this compound has the ability to act as a capable electron donor in a multilayer organic photovoltaic cell. The compound was synthesized through the use of a Kratschmer-Huffman arc reactor. A mixture of Praseodymium Oxide and …

One-Pot Γ-Amino Acids Synthesis From Co2 Via Zirconacycle, Teresita J. Maldonado, Diego A. Pedroza, Shizue Mito

COURI Symposium Abstracts, Summer 2012

One-pot γ-amino acids synthesis from CO₂ via zirconacycle was studied. It has been reported that ketone and isocyanides are viable substrates for insertion into Zr‒C bonds of zirconocene‒1-aza-1,3-diene complexes. The purpose of this project is to explore the viability of CO₂ insertion to develop a new method for γ-amino acids synthesis in which all the reactions are executed in a single pot. In this method, first zirconocene‒1-aza-1,3-diene complex is prepared by using Cp₂Zr₂Cl₂ and an α, β-unsaturated imine. Second, CO₂ was introduced into the zirconocene complex solution to form the seven-membered ring …

Development Of A New Protecting Group For N-Acetylneuraminic Acid In Glycopeptide Synthesis, Luis A. Barrera, Katja Michael

COURI Symposium Abstracts, Summer 2012

N-acetylneuraminc acid (Neu5Ac) is contained in a tumor-associated antigen called STn, which is expressed in form of glycoproteins on the cell surface of many carcinomas. Synthesized partial sequences (glycopeptides) of these cell surface glycoproteins could potentially be used as anticancer vaccines, or for the production of antibodies which could be useful for immunotherapy. STn-containing glycopeptides are sensitive to acid and base catalyzed decomposition, which makes their chemical synthesis quite challenging. If this research is successful, we may be able to contribute to the advancement of cancer research by making sensitive STn-containing glycopeptides more accessible through chemical synthesis.

My current project …

Synthesis Of Metal Organic Framework Composites For Improved Porosity, Jesse Murillo, Venkata P. Neti, Luis Echegoyen*

COURI Symposium Abstracts, Summer 2012

The synthesis of new highly porous composite materials, by combining Metal Organic Frameworks (MOFs) and graphene derivatives is described. The porosity of these composite materials is confirmed by pore volume, nitrogen uptake, BET and Langmuir surface area calculations. Structural information for the composites is accomplished through powder x-ray diffraction measurements, thermal gravimetric analysis and scanning electron microscopy. MOF-210, reported by Yaghi et al. in 2010, was chosen for composition with a graphene oxide composite due to its record holding pore size and internal surface area. The synthetic route to creation of precursors for MOF-210, as well as MOF-210 synthesis, is …

Dye-Sensitized Solar Cells, Laiwu Chen, Agustin Molina Ontoria, Luis A. Echegoyen

COURI Symposium Abstracts, Summer 2012

A dye-sensitized solar cell (DSSC) is a low-cost device for converting solar energy and possesses a large-area, flexible, colorful and lightweight devices. It is based on a semiconductor (TiO₂) deposited on a layer of conductive ITO glass. The dye is placed over this semiconductor film, in contact with an electrolyte in order to close the circuit .

The crucial requirements for dye-sensitized solar cells are: (a) wide absorption spectrum; (b) the right anchor to the TiO₂, for instance -COOH; (c) match the energy of the LUMO level of the photosensitizer with the Fermi level of the …

Synthesis Of Palmitoyl Dihydroxyacetonephosphate, Merieme Khamsi, Igor C. Almeida, Katja Michael

COURI Symposium Abstracts, Summer 2012

The parasite Trypanosoma cruzi (T. cruzi) causes Chagas disease which is a big problem in Central and South America, affecting 16-18 million people annually. While there are two non-FDA approved drugs to treat acute Chagas disease, there is no treatment available for its chronic stage. The objective of this project is to synthesize the substrate for acyl dihydroxyacetonephosphate synthase (ADS). This enzyme participates in the first step of alkyl lipid synthesis which is very abundant in T. cruzi, and is a potential target for developing more efficient drugs or inhibitors to treat Chagas disease. Recently, several alkyl phospholipid derivatives …

Solar Synthesis Of Acyl Hydroquinones And Their Bioactivity., Fernando De Leon, Shizue Mito

COURI Symposium Abstracts, Summer 2012

Without the Sun, we would not enjoy the benefits of life here on the Earth. This energy is essential and crucial for sustaining life: playing important roles in circadian rhythms and photosynthesis in plants. In our research, this endlessly renewable clean energy source is utilized for photo-Friedel-Crafts acylation of 1,4 - benzoquinones and 1,4 - naphthoquinones. Photo-Friedel-Crafts acylation was first discovered in 1891 and although there have been reported examples of acylated products, the substrates are still limited. In this project a variety of aldehydes having different substituents are examined, and bioassays were performed. While conventional methods for photochemistry use …

Photo-Switched Interfacial Layers For Organic Solar Cell Applications, Catalina Suárez, Danisha M. Rivera-Nazario, Mahsa Hosseini, Luis Echegoyen

COURI Symposium Abstracts, Summer 2012

Structural and functional diversity have been incorporated in photo-switched donor-acceptor (D-A) systems for the development and improvement of Organic Photovoltaic Cells (OPVs). By varying the structure and electronic properties of the donor and acceptor, the length and electronic properties of the linker, it is possible to control the efficiencies and lifetimes of photo-induced intramolecular charge separated states (D⁺-A^-). Modification of electrodes is a widely studied field for applications in biochemistry, materials science, electrocatalysis, among others. Here we report for the first time the modification of gold (Au) and indium tin oxide (ITO) electrodes with fullerene-based dyads …

Ti2s@C78: A Non-Group-Iii Metal Sulfide Cluster Inside A C78 Cage, Vivian L. Triana, Fang-Fang Li, Luis Echegoyen*

COURI Symposium Abstracts, Summer 2012

After the discovery of the first nitride cluster metallofullerenes (NCFs), Sc₃N@C₈₀, in 1999, numerous cluster metallofullerenes have been prepared. However, the types of “clusterfullerenes” reported so far are quite limited: nitride cluster fullerenes (NCFs), carbide cluster metallofullerenes (CCFs), oxide cluster metallofullerenes (OCFs) and sulfide cluster fullerenes (SCFs). Given that almost all of the encaged metals for all of these reported cluster fullerenes are limited to group-III (Sc, Y, and lanthanide) metals, there are very few reports of the synthesis of cluster fullerenes with a non-group III metal, titanium (Ti), trapped inside a carbon cage. However, the …

Synthesis Of Graphene/Mof-177 Composites, Nathaly Ortiz, Venkata P. Neti, Luis Echegoyen

COURI Symposium Abstracts, Summer 2012

Metal Organic Frameworks (MOFs) are formed by the self-assembly of metallic ions and organic ligands. These compounds have shown excellent properties for gas adsorption and catalytic activity. MOF-177 has one of the highest hydrogen storage capacities reported for porous materials at ambient temperatures (surface area = 3400m²/g), reported previously by Yaghi et al. Graphene and graphene based materials have unique structural, mechanical, and electronic properties. Graphene oxide(GO) and functionalized graphene have been used as support and as a structural pieces in the construction of MOF’s in the past. Synthesis of MOF-5 on the surface of GO and …

Novel Dyad-Fullerene Derivative Used As Acceptor With P3ht In Bulk Heterojunction Solar Cells, Amber D. Berkobien, Luis Echegoyen, Maira Cerón, Danisha Rivera

COURI Symposium Abstracts, Summer 2012

Within the world of solar cells, research is rapidly uncovering potential solutions to the alternative energy issues by utilizing bulk-heterojunction cell techniques (Figure 1a) for low-cost and quick effective manufacturing. In this scope of research, a unique concept of donor-acceptor (D-A) system pairing as an acceptor within the bulk-heterojunction cell has been brought to light; a new concept of utilizing HOMO/LUMO pairings to create effective transport systems between a combination D-A acceptor and polymer donor is being optimized for maximum Photo-Conversion Efficiency (PCE). Due to a similar band gap relationship between the commonly reported PCBM and the novel dyad fullerene …

Design, Synthesis And Evaluation Of Novel Diazirine Photolabels With Improved Ambient Light Stability And Fluorous-Based Enrichment Capacity, Arun Babu Kumar

USF Tampa Graduate Theses and Dissertations

Photoaffinity labeling is a quintessential technique in studying and analyzing the interaction between a ligand and receptor. Diazirines are one of the important photo-labile moieties used in photoaffinity labeling due to their superior photo labeling characteristics. Herein, we report the investigations we conducted with diazirine photolabels on (a) photochemical aspects leading to enhancement of their ambient light stability and (b) equipping them with fluorous tags to enable fluorous enrichment of labeled proteins. Furthermore, we report a pilot study to develop BACE-1 inhibitors, which have potential to be developed into photoaffinity probes.

3-Trifluoromethyl-3-phenyldiazirine offers good selectivity and protection against pseudolabeling but …

N-Acyl Ciprofloxacins: Synthesis, Antibacterial Activity And Effects On Molecular Loading Of Poly(Vinyl Benzoate) Nanoparticles, Ryan Cormier

USF Tampa Graduate Theses and Dissertations

Bacterial infections are becoming progressively more difficult to treat due to antibiotic resistance and the decreasing rate at which new antibiotics are brought to market. The Turos laboratory has attempted to tackle this problem for the last 15 years with the discovery of N-thiolated β-lactams leading to the design of polyacrylate nanoparticles to deliver these and other drugs. Chapter 1 discusses many reported instances of utilizing different types of polymeric nanoparticles to deliver antibiotics. Poly(lactic-co-glycolic acid) (PLGA), poly(alkyl cyanoacrylate) (PACA), poly(styrene-co-butylacrylate), and chitosan are the main polymers used to make nanoparticles. Chapter 2 describes the synthesis, antibacterial activity, and mechanism …

Synthetic Approaches To Organometallic Complexes For Electronics Applications, Ilya V. Vinogradov

Kaleidoscope

No abstract provided.

Design And Synthesis Of Protein-Protein Interaction Inhibitor Scaffolds, David B. Badger

USF Tampa Graduate Theses and Dissertations

Many currently relevant diseases such as cancer arise from altered biological pathways that rely on protein-protein interactions. The proteins involved in these interactions contain certain functional domains that are responsible for the protein's biological activities. These domains consist of secondary structural elements such as α-helices and Β-sheets which are at the heart of the protein's biological activity. Therefore, designing drugs that inhibit protein-protein interactions by binding to these key secondary structural elements should provide an effective treatment for many diseases. Presented in this dissertation are the designs, syntheses, and biological evaluations for both novel α-helix and novel Β-sheet mimics.

The …

The Importance Of The Rotor In Hydrazone-Based Molecular Switches, Xin Su, Timo Lessing, Ivan Aprahamian

Dartmouth Scholarship

The pH-activated E/Z isomerization of a series of hydrazone-based systems having different functional groups as part of the rotor (R = COMe, CN, Me, H), was studied. The switching efficiency of these systems was compared to that of a hydrazone-based molecular switch (R = COOEt) whose E/Z isomerization is fully reversible. It was found that the nature of the R group is critical for efficient switching to occur; the R group should be a moderate H-bond acceptor in order to (i) provide enough driving force for the rotor to move upon protonation, and (ii) stabilize the obtained Z configuration, to …

Design And Synthesis Of Novel Fluorescent Nucleoside Analogues, Nada Abdulnasir Elsharif

Electronic Theses and Dissertations

This project aimed to obtain a set of fluorescent nucleoside analogues that closely resemble cytosine with extending the aromatic surface (extended conjugation) for enhance the photophysical properties. In addition to synthesize new fluorescent nucleoside analogues and evaluate their photophysical properties, this project aimed to understand the effects of donor substituent on the tC photophysical properties.

The main goal of these studies is to develop highly fluorescent nucleotide analogues. We first were looking to synthesize tC^C fluorescent nucleotide with the pyrimido[4,5-b]quinolone. In this part, 2-chloro-3- formylquinoline was easily prepared, yet the cyclization of 2-chloro-3- formylquinoline with urea or guanidine HCl …

The Development Of Transparent, Processable, Thermally-Responsive Coatings, Christopher David Roland

Master's Theses

Polymer matrices are commonly used as guest-host systems for organic chromophores for use in non-linear optical materials. The chromophores must be aligned or poled in an electric field in order to impart anisotropy and non-linear activity to the material. This poling process raises several issues, the two largest being the eventual relaxation of the chromophores back into random orientations due to brownian motion, and high molecular weight polymer matrices limiting chromophore mobility during poling. The prevention of this relaxation process is an area of significant interest, especially in applications that require long term coating stability and activity. In this study, …

Lipid Peroxides And Glutathione Status In Human Progenitor Mononuclear (U937) Cells Following Exposure To Low Doses Of Nickel And Copper, William Y. Boadi, Shalandus Harris, Justin B. Anderson, Samuel E. Adunyah

Chemistry Faculty Research

Effects of Cu2+, Ni2+ or Cu2+ + Ni2+ on lipid peroxide and glutathione (GSH) levels in U937 cells were investigated. Cells were treated with 0, 5, 10, and 20 µM of Cu2+ and/or Ni2+ and H2O2 (0.01 mM) and incubated for 24 hours at 37°C. Lipid peroxides were measured by the thiobarbituric acid assay (TBA). GSH intracellular levels were assayed by the GSH assay kit from EMD/Calbiochem (San Diego, California, USA). Cu2+ or Ni2+ significantly (P < 0.01) increased lipid peroxides in a dose-dependent manner, compared to controls. The effect was more pronounced for Cu2+, compared to the Ni2+-treated samples. Cu2+ + Ni2+ increased lipid peroxides in a significant (P < 0.001), dose-dependent manner, compared to Cu2+ or Ni2+ alone (i.e., ratio of 2.5:1-fold for combined versus single treatments, respectively). Cu2+ or Ni2+ significantly decreased GSH levels in U937 cells, with the effect being pronounced for Cu2+. Cu2+ + Ni2+ metal ions significantly (P < 0.001) depleted cells of GSH in a dose-dependent manner. Ethylene diamine tetraacetic acid (EDTA) at 50 or 100 µM moderately reduced the Cu2+- or Ni2+-induced effects on GSH levels. Interestingly, GSH levels generally decreased to half (except for the combined metal dose of 20 µM at 100 µM EDTA) of its level at the highest metal concentration tested for both the single or combined treatments. In conclusion, multiple exposures of cells to metal ions may be lethal to cells, compared to their single treatments.

Electronic Properties Of Memantine (Alzheimer's Disease) And Amantadine (Anti-Flu) Drugs, Kirsten Middleton, Guo-Ping Zhang, Thomas F. George

Symposium 2012

Alzheimer’s Disease is the 5th leading cause of death for Americans 65 and older Treatment The U.S. Food and Drug Administration Only five drugs approved that “temporarily slow worsening of symptoms for about six to 12 months.” Effective for only about half of all patients.

Synthesis And Biological Evaluation Of Rigid Analogues Of Methamphetamines, Andrea N. Forsyth

LSU New Orleans Theses and Dissertations

A series of rigid azetidenyl-based methamphetamine analogs were synthesized from commercially available N-Boc-azetidinone. The benzylideneazetidine analogs were prepared via a Wittig olefination via the ylides generated from the corresponding triphenylphosphonium benzylhalide salts. The substituted benzylazetidine analogs were synthesized from the corresponding benzylideneazetidienes via hydrogention over palladium and platinum catalysts. The benzylideneazetidine and benzyliazetidine analogs were evaluated at monoamine transporters as a part of preliminary structure-activity study for the development of novel monoamine transporter ligands. The binding affinities of the azetidine analogs were determined at dopamine (DAT) and serotonin (SERT) transporters in rat brain tissue preparations. The preliminary in vitro …

Synthesis And Development Of Potential Cb1 Receptor Neutral Antagonists, Kimari Slaughter

LSU New Orleans Theses and Dissertations

Cannabis and its derivatives have been used for both medicinal and recreational purposes. The study of this plant led to the discovery of over 60 cannabinoids, found exclusively in cannabis, that contribute to the behavioral effects of cannabis use, the most common is delta-9-tetrahydrocannabinol. Cannabinoid receptors function to increase activity in the mesolimbic dopamine reward system. Dopamine is a neurotransmitter that plays a major role in addition and its regulation plays a crucial role in mental and physical well-being. There is evidence that CB₁ receptors are important to the reinforcing effects and the development of physical dependence on opiate …

Synthesis And Characterization Of Sugar Based Low Molecular Weight Gelators, Hao Yang

LSU New Orleans Theses and Dissertations

Low molecular weight gelators (LMWGs) have gained great attention over the past two decades. These compounds form self-assembled fibrous networks like micelles, cylindrical, sheets, fibers, layers and so on. The fibrous network entraps the solvent and form gel. LMWGs are interesting compounds with many potential applications in material and biomedical sciences.

Many different structures have been found to be good LMWGs. Our interests focus on the carbohydrate based LMWGs. Previously, we have found that several ester derivatives of methyl 4, 6-O-benzylidene-α-D-glucopyranoside are good gelators for organic solvents and aqueous solutions. In this study, in order to understand the …

Synthesis Of S-Ribosyl-L-Homocysteine And Analogs Modified At The Homocysteine-C3 Position, Ruoyi Liu

Master's Theses

Quorum sensing (QS) is a process of bacterial cell-to-cell communication that conveys population density information in order to coordinate gene expression to produce synchronized behaviors. QS regulates the expression of virulence genes in many species of bacteria; hence, the manipulation of QS pathways may lead to treatment options against many bacterial diseases. The LuxS enzyme converts S-ribosyl-L-homocysteine (SRH) into homocysteine (HCys) and 4(S),5-dihydroxypentane-2,3-dione (DPD), which is the precursor of autoinducer-2 (AI-2). Thus, inhibitors of LuxS could prevent QS by halting the conversion of SRH to AI-2 rendering the cell “uncommunicative”. This work shows the successful chemical synthesis …

Chiral Recognition In Amino Acid And Peptide Based Chiral Ionic Liquids, Daniel Mccray Kroupa

Undergraduate Honors Thesis Collection

In this study, amino acid and peptide based chiral ionic liquids (ILs) were prepared and their chiral recognition ability probed using circularly polarized luminescence (CPL) spectroscopy. Potential applications of amino acid and peptide based chiral ILs include asymmetric synthesis and chiral resolution. The amino acid based chiral ILs under study were prepared from amino acid methyl ester cations and bis(trifluoromethane)sulfonamide ([TF2ND anions, specifically L-alanine methyl ester, D-alanine methyl ester, L-Ieucine methyl ester, and L-proline methyl ester. Cationic peptide ILs were prepared from L-alanyl glycine methyl ester cations and [TF2Nr anions and anionic peptide based ILs were prepared from tetrabutylammonium ([TBAt) …

Design And Synthesis Of Solid State Materials Constructed From Polyoxomolybdate Clusters, Stephanie Jones

Chemistry - Dissertations

This work encompasses detailed investigations of the synthesis and structures of polyoxomolybdate materials. The design and synthesis of hybrid organic-inorganic materials constructed from various anionic polyoxomolybdate units and cationic secondary metal-ligand units, and the synthesis and ligand-exchange capacity of the giant polyoxomolybdate cluster Mo-132 are described. These studies aim to increase our understanding of the formation and physiochemical properties of these materials, and thereby aid in the ability to control and predict their structural chemistry.

The analysis of a number of structural determinants in the oxomolybdenum-organodiphosphonate system aims to expand the current knowledge of this family of materials. We have …

Synthesis, Structure, And Characterization Of Hybrid Solids Containing Polyoxometalates And Ruthenium Polypyridyl Complexes, Yanfen Ll

Masters Theses & Specialist Projects

Polyoxometalates (POMs), which are inorganic metal oxide cluster anions with discrete structures, have been extensively studied in recent years due to their large variety of applications such as medicine, biology, catalysis, material sciences and chemical analysis. Ruthenium polypyridyl complexes have been extensively studied for their applications as photosensitizers in solar energy conversion and photoelectronic materials. Recently, ruthenium heterocyclic ligand complex-based building blocks have been used for the synthesis of hybrid organic-inorganic solids through the self-assembly. We are interested in the synthesis of ruthenium polypyridyl complexes and polyoxometalate anions through different ways such as coordination bonds, hydrogen bonds and ionic bonds …

Sprectral Data For "Generation Of Molecular Complexity From Cyclooctatetraene Using Dienyliron And Olefin Metathesis", Mohamed F. El-Mansy, Anobick Sar, Subhabrata Chaudhury, Nathaniel J. Wallock, William A. Donaldson

Natural Products Synthesis via Organoiron Methodology

Spectral data used in the course of researching "Generation of molecular complexity from cyclooctatetraene using dienyliron and olefin metathesis methodology".

Transformation of the simple hydrocarbon cyclooctatetraene into a variety of polycyclic skeletons was achieved by sequential coordination to iron, reaction with electrophiles followed by allylated nucleophiles, decomplexation and olefin metathesis.

The Reaction Of Methionine With A Non-C2-Symmetrical Platinum (Ii) Diamine Compound, Nilesh Sahi

Mahurin Honors College Capstone Experience/Thesis Projects

The research that we have conducted has allowed us to discover that the amino acids, methionine (Met) and N-acetyl methionine (N-AcMet), will react in a 1:1 and 1:2 molar ratio with platinum complexes containing bulky diamine ligands. Previous research has allowed us to gain a plethora of information on the experimentation and results of specific bulky diamine ligands such as N,N,N',N'-tetramethylethylenediamine and N,N-diethylethylenediamine. In the current study, we have investigated the bulky diamine ligand of N,N-dimethylethylenediamine, or Me₂en. With our focus on the bulk of the Me₂en ligand, we have been able to synthesize a platinum …

Oxaliplatin And Oxaliplatin Derivatives: Synthesis, Characterization, And Reactivity With Biologically Relevant Ligands, Amy Poynter

Mahurin Honors College Capstone Experience/Thesis Projects

Oxaliplatin is a third generation anticancer drug that has proven to be successful in fighting ovarian and testicular cancer. We are interested in determining how oxaliplatin and oxaliplatin derivatives interact with proteins, as well as how that interaction is affected by the size and shape of these platinum compounds. We have synthesized oxaliplatin as it is used in cancer treatment, as well as similar platinum compounds with the same diaminocyclohexane ligand as oxaliplatin but with additional bulk added to the nitrogen atoms. We are reacting oxaliplatin with key amino acids, including methionine, and will be comparing the kinetics of this …